Summary: This journal is c the Owner Societies 2011 Phys. Chem. Chem. Phys.
Cite this: DOI: 10.1039/c1cp21077g
Initial stages of salt crystal dissolution determined with ab initio
molecular dynamicsw
Li-Min Liu,a
Alessandro Laiob
and Angelos Michaelides*a
Received 6th April 2011, Accepted 11th May 2011
DOI: 10.1039/c1cp21077g
The initial stages of NaCl dissolution in liquid water have been
examined with state-of-the-art ab initio molecular dynamics and
free energy sampling techniques. Our simulations reveal a complex
multi-step process triggered by the departure of Cl ions from the
lattice, with a well-defined intermediate state wherein departing
ions are partially solvated but remain in contact with the crystal.
The polarizability of ClĄ
is identified as the source of the anion's
preferential initial dissolution, an effect which leads a forcefield
based description of NaCl dissolution to fail to identify a preference
for Cl over Na dissolution.